EP4313566A1 - Procédé de fabrication de lentilles de contact en hydrogel incorporées - Google Patents

Procédé de fabrication de lentilles de contact en hydrogel incorporées

Info

Publication number
EP4313566A1
EP4313566A1 EP22713749.4A EP22713749A EP4313566A1 EP 4313566 A1 EP4313566 A1 EP 4313566A1 EP 22713749 A EP22713749 A EP 22713749A EP 4313566 A1 EP4313566 A1 EP 4313566A1
Authority
EP
European Patent Office
Prior art keywords
meth
contact lens
hydrogel contact
embedded
lens
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22713749.4A
Other languages
German (de)
English (en)
Inventor
Richard Charles Breitkopf
Zahra BASSAMPOUR
Chandana Kolluru
Steve Yun ZHANG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alcon Inc
Original Assignee
Alcon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alcon Inc filed Critical Alcon Inc
Publication of EP4313566A1 publication Critical patent/EP4313566A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/0048—Moulds for lenses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14065—Positioning or centering articles in the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00048—Production of contact lenses composed of parts with dissimilar composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00125—Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
    • B29D11/00134—Curing of the contact lens material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00125—Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
    • B29D11/00192—Demoulding, e.g. separating lenses from mould halves
    • B29D11/00221—Demoulding, e.g. separating lenses from mould halves using prying means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00317—Production of lenses with markings or patterns
    • B29D11/00346—Production of lenses with markings or patterns having nanosize structures or features, e.g. fillers
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00067—Hydrating contact lenses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00807—Producing lenses combined with electronics, e.g. chips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2633/00—Use of polymers of unsaturated acids or derivatives thereof for preformed parts, e.g. for inserts
    • B29K2633/04—Polymers of esters
    • B29K2633/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2715/00—Condition, form or state of preformed parts, e.g. inserts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention generally relates to a method for producing embedded hydrogel contact lenses.
  • the present invention provides embedded hydrogel contact lenses produced according to a method of the invention.
  • BACKGROUND Hydrogel contact lenses are widely used for correcting many different types of vision deficiencies due to their softness for wearing comfort. They are made of a hydrated, crosslinked polymeric material that contains from about 20% to about 75% by weight of water within the lens polymer matrix at equilibrium. Hydrogel contact lenses generally are produced according to the conventional full cast-molding process.
  • Such a conventional manufacturing process comprises at least the following steps: lens molding (i.e., curing a polymerizable composition in lens molds), demolding (i.e., removing lenses from molds), extracting lenses with an extraction medium, hydrating lenses, packaging and sterilizing the hydrated lenses.
  • lens molding i.e., curing a polymerizable composition in lens molds
  • demolding i.e., removing lenses from molds
  • extracting lenses with an extraction medium e.e., removing lenses from molds
  • the hydrogel contact lenses will absorb water and typically can swell significantly in size.
  • various inserts can be incorporated in hydrogel contact lenses for various purposes, e.g., for corneal health, vision correction, diagnosis, etc. See, for example, U.S. Pat.
  • a typical approach is to use molds having positioning guides (posts) provided on their molding surface for cast-molding embedded hydrogel contact lenses. Those positioning guides (posts) provides means for precisely positioning inserts in molds during cast-molding process. However, by using such molds with positioning guides (posts), small holes derived from those positioning guides (posts) are formed in resultant embedded hydrogel contact lenses. Those small holes in the embedded hydrogel lenses are susceptible to bioburden trapping.
  • the invention provides a method for producing embedded hydrogel contact lenses, the method of invention comprising the steps of: (1) obtaining a magnetized insert which comprises a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the insert is made of a polymeric material and comprises magnetic particles; (2) obtaining a lens mold, wherein the lens mold comprises a female mold half having a first molding surface and a male mold half having a second molding surface, wherein the female and male mold halves are configured to receive each other such that a mold cavity is formed between the first and second molding surfaces when the mold is closed; (3) in no particular order, placing the magnetized insert in the lens mold and introducing a lens-forming composition in the lens mold, wherein the magnetized insert is immersed in the lens-forming composition
  • the invention provides an embedded hydrogel contact lens, comprising: an anterior surface, an opposite posterior surface, a bulk hydrogel material, and a magnetized insert embedded in the bulk hydrogel material, wherein the magnetized insert is made of a polymeric material and comprises magnetic particles, wherein the magnetized insert has a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the magnetized insert is located in a central portion of the embedded hydrogel contact lens, wherein the embedded hydrogel contact lens is not susceptible to delamination as demonstrated by being free of bubble that can be observed under microscopy at interfaces between the insert and the bulk material within the embedded silicone hydrogel contact lens after being autoclaved in a packaging solution in a sealed package, wherein the packaging solution is a buffered saline having a pH of 7.1 ⁇ 0.2.
  • Figure 1 shows images of the unprocessed embedded SiHy contact lens obtained before opening the mold: 1A – comprising a magnetized insert that is centered and formed from an insert-forming composition including 1% by weight of magnetite; 1B (Control) – comprising a non-magnetized insert that is decentered and formed from an insert-forming composition free of any magnetite.
  • 1A – comprising a magnetized insert that is centered and formed from an insert-forming composition including 1% by weight of magnetite
  • 1B (Control) – comprising a non-magnetized insert that is decentered and formed from an insert-forming composition free of any magnetite.
  • DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature used herein and the laboratory procedures are well known and commonly employed in the art.
  • Contact Lens refers to a structure that can be placed on or within a wearer's eye. A contact lens can correct, improve, or alter a user's eyesight, but that need not be the case.
  • a contact lens can be of any appropriate material known in the art or later developed, and can be a soft lens, a hard lens, or an embedded lens.
  • a “hydrogel contact lens” refers to a contact lens comprising a hydrogel bulk (core) material.
  • a hydrogel bulk material can be a non-silicone hydrogel material or preferably a silicone hydrogel material.
  • a “hydrogel” or “hydrogel material” refers to a crosslinked polymeric material which has three-dimensional polymer networks (i.e., polymer matrix), is insoluble in water, but can hold at least 10% by weight of water in its polymer matrix when it is fully hydrated (or equilibrated).
  • a siloxane which often also described as a silicone, refers to a molecule having at least one moiety of –Si–O–Si– where each Si atom carries two organic groups as substituents.
  • a “silicone hydrogel” or “SiHy” refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing monomer or at least one silicone-containing macromer or at least one crosslinkable silicone- containing prepolymer.
  • the term “non-silicone hydrogel” or “non-silicone hydrogel material” interchangeably refers to a hydrogel that is theoretically free of silicon.
  • a “male mold half” or “base curve mold half” interchangeably refers to a mold half having a molding surface that is a substantially convex surface and that defines the posterior (back) surface of a contact lens (or an insert).
  • a “female mold half” or “front curve mold half” interchangeably refers to a mold half having a molding surface that is a substantially concave surface and that defines the anterior (front) surface of a contact lens (or an insert).
  • the anterior surface (front surface) is typically substantially convex.
  • the posterior surface (back surface) is typically substantially concave.
  • An “embedded hydrogel contact lens” refers a hydrogel contact lens comprising at least one insert which is embedded fully or partially within the bulk hydrogel material of the embedded hydrogel contact lens.
  • an “insert” refers to any preformed article which has a diameter of up to 13 mm, a front (anterior) surface, an opposite back (posterior) surface, and a thickness less than any thickness of an embedded hydrogel contact lens in the region where the insert is embedded.
  • the insert must be smaller than the embedded hydrogel contact lens in dimension, so as to be embedded in the bulk material of the embedded hydrogel contact lens.
  • the insert can be made of a polymeric material that can be a non- hydrogel material or a hydrogel material.
  • preferred inserts include without limitation thin rigid inserts for providing rigid center optics for masking astigmatism like a rigid gas permeable (RGP) contact lens, multifocal lens inserts, photochromic inserts, cosmetic inserts having color patterns printed thereon, etc.
  • a non-hydrogel material can be any material that can absorb less than 5% (preferably about 4% or less, more preferably about 3% or less, even more preferably about 2% or less) by weight of water when being fully hydrated.
  • “Hydrophilic,” as used herein, describes a material or portion thereof that will more readily associate with water than with lipids.
  • room temperature refers to a temperature of about 22°C to about 26°C.
  • soluble in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent to give a solution with a concentration of at least about 0.5% by weight at room temperature (i.e., a temperature of about 22°C to about 26°C).
  • insoluble in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent to give a solution with a concentration of less than 0.01% by weight at room temperature (as defined above).
  • a “vinylic monomer” refers to a compound that has one sole ethylenically unsaturated group, is soluble in a solvent, and can be polymerized actinically or thermally.
  • An “acrylic monomer” refers to a vinylic monomer having one sole (meth)acryloyl group. Examples of acrylic monomrs includes (meth)acryloxy [or(meth)acryloyloxy] monomers and (meth)acrylamido monomers.
  • an “(meth)acryloxy monomer” or “(meth)acryloyloxy monomer” refers to a vinylic monomer having one sole group of An “(meth)acrylamido monomer” refers to a vinylic monomer having one sole group of in which R o is H or C 1 -C 4 alkyl.
  • aryl acrylic monomer refers to an acrylic monomer having at least one aromatic ring.
  • An “(meth)acryloxy monomer” or “(meth)acryloyloxy monomer” refers to a vinylic monomer having one sole group of An “(meth)acrylamido monomer” refers to a vinylic monomer having one sole group of in which R o is H or C 1 -C alkyl.
  • (meth)acrylamide refers to methacrylamide and/or acrylamide.
  • (meth)acrylate refers to methacrylate and/or acrylate.
  • An “N-vinyl amide monomer” refers to an amide compound having a vinyl group that is directly attached to the nitrogen atom of the amide group.
  • An “ene monomer” refers to a vinylic monomer having one sole ene group.
  • An “ene group” refers to a group of or that is not directly linked to a nitrogen atom, an oxygen atom or a carbonyl group.
  • the term “vinylic crosslinker” refers to an organic compound having at least two ethylenically unsaturated groups.
  • a “vinylic crosslinking agent” refers to a vinylic crosslinker having a molecular weight of 700 Daltons or less.
  • An “acrylic crosslinker” refers to a vinylic crosslinker having at least two (meth)acryloyl groups.
  • the term “acrylic repeating units” refers to repeating units of a polymeric material, each of which is derived from an acrylic monomer or crosslinker in a free-radical polymerization to form the polymeric material.
  • terminal (meth)acryloyl group refers to one (meth)acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound as known to a person skilled in the art.
  • actinically in reference to curing, crosslinking or polymerizing of a polymerizable composition, a prepolymer or a material means that the curing (e.g., crosslinked and/or polymerized) is performed by actinic irradiation, such as, for example, UV/visible irradiation, ionizing radiation (e.g. gamma ray or X-ray irradiation), microwave irradiation, and the like.
  • actinic irradiation such as, for example, UV/visible irradiation, ionizing radiation (e.g. gamma ray or X-ray irradiation), microwave irradiation, and the like.
  • thermal curing or actinic curing methods are well-known to a person skilled in the art.
  • polymer means a material formed by polymerizing/crosslinking one or more monomers or macromers or prepolymers or combinations thereof.
  • a “macromer” or “prepolymer” refers to a compound or polymer that contains ethylenically unsaturated groups and has a number average molecular weight of greater than 700 Daltons.
  • molecular weight of a polymeric material refers to the number-average molecular weight unless otherwise specifically noted or unless testing conditions indicate otherwise.
  • GPC gel permeation chromatography
  • a “polysiloxane segment” or “polydiorganosiloxane segment” interchangeably refers to a polymer chain segment (i.e., a divalent radical) of n which SN is an integer of 3 or larger and each of R S1 and R S2 independent of one another are selected from the group consisting of: C 1 -C 10 alkyl; phenyl; C 1 -C 4 -alkyl-substituted phenyl; C 1 -C 4 -alkoxy- substituted phenyl; phenyl-C 1 -C 6 -alkyl; C 1 -C 10 fluoroalkyl; C 1 -C 10 fluoroether; aryl; aryl C 1 -C 18 alkyl; –alk–(OC 2 H 4 ) ⁇ 1 –OR o (in which alk is C 1 -C 6 alkylene diradical, R o is H or C 1 -C 4 alkyl and
  • a “polysiloxane vinylic monomer” refers to a compound comprising at least one polysiloxane segment and one sole ethylenically-unsaturated group.
  • a “polydiorganosiloxane vinylic crosslinker” or polysiloxane vinylic crosslinker” interchangeably refers to a compound comprising at least one polysiloxane segment and at least two ethylenically-unsaturated groups.
  • a “linear polydiorganosiloxane vinylic crosslinker” or “linear polysiloxane vinylic crosslinker” interchangeably refers to a compound comprising a main chain which includes at least one polysiloxane segment and is terminated with one ethylenically-unsaturated group at each of the two ends of the main chain.
  • a “chain-extended polydiorganosiloxane vinylic crosslinker” or “chain-extended polysiloxane vinylic crosslinker” interchangeably refers to a compound comprising at least two ethylenically-unsaturated groups and at least two polysiloxane segments each pair of which are linked by one divalent radical.
  • fluid indicates that a material is capable of flowing like a liquid.
  • the term “clear” in reference to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture (i.e., having a light transmissibility of 85% or greater, preferably 90% or greater in the range between 400 to 700 nm).
  • monovalent radical refers to an organic radical that is obtained by removing a hydrogen atom from an organic compound and that forms one bond with one other group in an organic compound.
  • Examples include without limitation, alkyl (by removal of a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removal of one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removal of one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removal of a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removal of a hydrogen atom from a cycloheteroalkane), aryl (by removal of a hydrogen atom from an aromatic ring of the aromatic hydrocarbon), heteroaryl (by removal of a hydrogen atom from any ring atom), amino (by removal of one hydrogen atom from an amine), etc.
  • divalent radical refers to an organic radical that is obtained by removing two hydrogen atoms from an organic compound and that forms two bonds with other two groups in an organic compound.
  • an alkylene divalent radical i.e., alkylenyl
  • a cycloalkylene divalent radical i.e., cycloalkylenyl
  • cyclic ring is obtained by removal of two hydrogen atoms from the cyclic ring.
  • substituted in reference to an alkyl or an alkylenyl means that the alkyl or the alkylenyl comprises at least one substituent which replaces one hydrogen atom of the alkyl or the alkylenyl and is selected from the group consisting of hydroxyl (-OH ), carboxyl (-COOH), -NH 2 , sulfhydryl (-SH), C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio (alkyl sulfide), C 1 -C 4 acylamino, C 1 -C 4 alkylamino, di-C 1 -C 4 alkylamino, and combinations thereof.
  • a free radical initiator can be either a photoinitiator or a thermal initiator.
  • a “photoinitiator” refers to a chemical that initiates free radical crosslinking/polymerizing reaction by the use of light.
  • a “thermal initiator” refers to a chemical that initiates free radical crosslinking/polymerizing reaction by the use of heat energy.
  • the “oxygen permeability”, Dk i , of a material is the rate at which oxygen will pass through a material and can be measured at about 34-35°C according to the procedures described in Example 1.
  • Oxygen permeability is conventionally expressed in units of barrers, where “barrer” is defined as [(cm 3 oxygen)(mm) / (cm 2 )(sec)(mm Hg)] x 10 -10 .
  • the “oxygen transmissibility”, Dk/t, of an insert or material is the rate at which oxygen will pass through a specific insert or material with an average thickness of t [in units of mm] over the area being measured.
  • Oxygen transmissibility is conventionally expressed in units of barrers/mm, where “barrers/mm” is defined as [(cm 3 oxygen)/(cm 2 )(sec)(mm Hg)] x 10 -9 .
  • modulus or “elastic modulus” in reference to a contact lens or a material means the tensile modulus or Young's modulus which is a measure of the stiffness of a contact lens or a material.
  • the modulus can be measured according to the procedures described in Example 1.
  • An “unprocessed state” refers to an insert which is obtained by cast-molding of a polymerizable composition in a mold and has not been subjected to extraction and/or hydration post-molding processes (i.e., having not been in contact with water or any organic solvent or any liquid after molding).
  • the invention is directed to a method for producing embedded hydrogel contact lenses having an insert that is embedded completely or partially in the bulk hydrogel material of the embedded hydrogel contact lens and comprises magnetic particles.
  • This invention is based on the discovery that an insert having magnetic particles thereon and therein (i.e., a magnetized insert) can be centered or positioned in any desired position in a lens mold for molding a contact lens by using a magnet placed below the lens mold.
  • a magnetized insert in combination with a magnet, the accurately positioning of inserts during molding in a method of the invention can be achieved.
  • the use of magnetized insert can simplify the process for producing embedded hydrogel contact lenses and enable the process to be implemented readily in an automatic production.
  • a method of the invention can avoid the use of positioning guides (posts) and eliminate holes derived from the positioning guides (posts), thereby eliminating protein and/or bioburden buildup in those holes in the embedded hydrogel contact lenses.
  • the invention provides a method for producing embedded hydrogel contact lenses, the method of invention comprising the steps of: (1) obtaining a magnetized insert which comprises a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the insert is made of a polymeric material and comprises magnetic particles; (2) obtaining a lens mold, wherein the lens mold comprises a female mold half having a first molding surface and a male mold half having a second molding surface, wherein the female and male mold halves are configured to receive each other such that a mold cavity is formed between the first and second molding surfaces when the mold is closed; (3) in no particular order, placing the magnetized insert in the lens mold and introducing a lens-forming composition in the lens mold, wherein the magnetized insert is immersed in the lens-forming composition in the lens mold and
  • the invention provides an embedded hydrogel contact lens, comprising: an anterior surface, an opposite posterior surface, a bulk hydrogel material, and a magnetized insert embedded in the bulk hydrogel material, wherein the magnetized insert is made of a polymeric material and comprises magnetic particles, wherein the magnetized insert has a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the magnetized insert is located in a central portion of the embedded hydrogel contact lens, wherein the embedded hydrogel contact lens is not susceptible to delamination as demonstrated by being free of bubble that can be observed under microscopy at interfaces between the insert and the bulk material within the embedded silicone hydrogel contact lens after being autoclaved in a packaging solution in a sealed package, wherein the packaging solution is a buffered saline having a pH of 7.1 ⁇ 0.2.
  • Mold halves for making contact lenses (or inserts) are well known to a person skilled in the art and, for example, are employed in cast molding.
  • a molding assembly comprises at least two mold halves, one male half and one female mold half.
  • the male mold half has a first molding (or optical) surface which is in direct contact with a polymerizable composition for cast molding of a contact lens (or an insert) and defines the posterior (back) surface of a molded contact lens (or a molded insert); and the female mold half has a second molding (or optical) surface which is in direct contact with the polymerizable composition and defines the anterior (front) surface of the molded contact lens (or molded insert).
  • the male and female mold halves are configured to receive each other such that a lens- or insert-forming cavity is formed between the first molding surface and the second molding surface.
  • Methods of manufacturing mold halves for cast-molding a contact lens or an insert are generally well known to those of ordinary skill in the art.
  • the process of the present invention is not limited to any particular method of forming a mold half. In fact, any method of forming a mold half can be used in the present invention.
  • the mold halves can be formed through various techniques, such as injection molding or lathing. Examples of suitable processes for forming the mold halves are disclosed in U.S. Pat. Nos.4444711; 4460534; 5843346; and 5894002.
  • a “magnetized insert” refers to an insert comprising magnetic particles therein and/or thereon. Any magnetic particles can be used in the invention.
  • Nano- and micro-sized magnetic particles are well known in the art and have been used in magnetic particles imaging (MPI), separation and inspections as well as in the biomedical, energy, electronic and environmental fields (see, Colloidal Metal Oxide Nanoparticles: Synthesis, Characterization and Applications (Metal Oxides), Ed. by S Thomas, A.T. Sunny and P. Velayudhan, Elsevier; 1 st Edition (September 15, 2019)).
  • Magnetic particles with a wide range of particles sizes can be obtained from commercial sources, e.g., Chemcell GmbH (Berlin, Germany), Creative Diagnostics (Shirley, NY), etc. or can be prepared according any methods known to person skilled in the art (see, e.g., U.S. Pat.
  • a magnetized insert is made of a polymeric material and comprises magnetic particles distributed in the polymeric material.
  • This type of magnetized inserts can be obtained by cast-molding of an insert-forming composition (i.e., a polymerizable composition for molding inserts) comprising magnetic particles.
  • a magnetized insert is made of a polymeric material and has a magnetic coating thereon. This type of magnetized inserts can be obtained by applying a magnetic coating composition onto one of the front and back surface of a preformed insert.
  • a magnetic coating composition comprises magnetic particle and can be prepared by adding the magnetic particles in any coating composition known to a person skilled in the art.
  • a magnetic insert is made of a polymeric material and comprises a magnetic color image thereon.
  • a “magnetic color image” refers to any cosmetic patterns, for example, annular rings (e.g., as shown in Figs.1-6 of US8770747, Figs.1-7 of US9039173, and Figs.1-8 of US10156736, simulated iris patterns (e.g., as shown in U.S. Pat.
  • Wild Eye TM patterns which are printed onto one of the front and back surfaces of a preformed insert with an ink comprising magnetic particles.
  • Any inks can be used in the invention, so long as they comprise magnetic particles.
  • an ink comprises pigment particles and at least one binder polymer and a solvent.
  • Pad transfer printing is well known in the art (see. For example, United States Patent Nos.3,536,386 to Spivack; 4,582,402 and 4,704,017 to Knapp; 5,034,166 to Rawlings et al., herein incorporated by reference in their entireties).
  • a typical example of this printing follows. An image is etched into metal to form a cliché. The cliché is placed in a printer. Once in the printer, the cliché is inked by either an open inkwell doctoring system or by a closed ink cup sliding across the image.
  • a silicone pad picks up the inked image from the cliché and transfers the image to the contact lens.
  • the silicone pads are made of a material comprising silicone that can vary in elasticity. The properties of the silicone material permit the inks to stick to the pad temporarily and fully release from the pad when it contacts a preformed insert or a mold for molding an insert.
  • Appropriate pad-transfer printing structures include, but are not limited to, Tampo-type printing structures (Tampo vario 90/130), rubber stamps, thimbles, doctor's blade, direct printing, or transfer printing as they are known in the art. Any known suitable silicone pad can be used in the present invention. Silicone pads are commercially available. However, different pads could give different print qualities.
  • Clichés can be made of ceramics or metals (e.g., steel). Where a cliché is made of a steel, it would be desirable to neutralize the pH of a water-based ink (e.g., adjusted pH to 6.8 ⁇ 7.8) by adding a buffer (such as, for example, phosphate salts). Images can be etched into a cliché according to any methods known to a person skilled in the art, for example, by chemical etching or laser ablation or the like. It is also desirable to clean clichés after use using standard cleaning techniques known to a person skilled in the art, such as, for example, immersion in a solvent, sonication, or mechanical abrasion.
  • either the front surface and/or the back surface of the preformed insert may be printed.
  • a preformed insert having a magnetic color image thereon can be made according to a print-on-mold process similar to those described in U.S. Pat. No.5034166.
  • An ink can be applied first on the molding surface of one or both mold halves by using pad transfer printing (or pad printing) or inkjet printing to form a magnetic colored coat (with a magnetic color image).
  • a magnetic colored coat can be applied on a molding surface defining the front or back surface of an insert to be molded or on both the molding surfaces defining the front and back surfaces respectively of an insert to be molded.
  • the printed ink can be cured thermally or actinically. It is desirable that the printed ink is cured actinically to an extent to minimize loss of pattern definition of the magnetic color image resulted from subsequent filling of an insert-forming composition.
  • an insert-forming composition is introduced in the mold comprising the magnetic color image printed on the molding surface and subsequently cured to form the magnetic insert having a magnetic color image on one of the front and back surfaces thereof.
  • a magnetized insert is made of a hard plastics (preferably a crosslinked polymethylmethacrylate).
  • a magnetized insert is made of a crosslinked silicone polymer (or a silicone rubber or elastomer as known to a person skilled in the art).
  • a crosslinked silicone material has three-dimensional polymer networks (i.e., polymer matrix), is insoluble in water, and has an equilibrium water content of about 5% or less, preferably about 3% or less, more preferably about 2% or less) by weight (i.e., in fully-hydrated state).
  • a magnetized insert is made of a non-silicone hydrogel material (any one of those described later in this application).
  • a magnetized insert is made of a silicone hydrogel material (any one of those described later in this application).
  • a magnetized insert is made of a rigid gas permeable material (e.g., a material made from fluorosilicone acrylates).
  • a magnetized insert comprises repeating units of at least one polymerizable photochromic compound (i.e., at least one photochromic vinylic monomer), at least one UV-absorbing vinylic monomer, at least one UV/HEVL-absorbing vinylic monomer, a fluorescent vinylic monomer, or combinations thereof.
  • a magnetized insert comprises at least one photochromic dye or pigment, at least one color-filtering material for correcting color blindness, a diffractive material, a high refractive-index material, or combinations.
  • a magnetized insert is made of a hydrophobic crosslinked acrylic material that has an equilibrium water content of less than 5% by weight and comprises at least about 55% (preferably at least about 60%, more preferably at least about 65% even more preferalby at least about 70%) by mole of repeating units of one or more acrylic monomers and/or one or more acrylic crosslinker or crosslinking agent and at least about 6% by mole (preferably at least about 8% by mole, more preferably at least about 10% by mole, even more preferably at least about 12% by mole) of repeating units at least one vinylic crosslinking agent.
  • Any hydrophobic acrylic monomers can be used in forming a hydrophobic material of the inventions.
  • hydrophobic acrylic monomers examples include silicone-containing acrylic monomers (any one of those described below in this application), non-silicone hydrophobic acrylic monomers (any one of those described below in this application), fluorine-containing acrylic monomers (any one of those described below in this application), aryl acrylic monomers as described below, and combinations thereof.
  • aryl acrylic monomers of formula (I) examples include, but are not limited to those described later in this application.
  • Aryl acrylic monomers of formula (I) can be obtained from commercial sources or alternatively prepared according to methods known in the art.
  • Preferred aryl acrylic monomers of formula (I) are those wherein B 1 is OCH 2 CH 2 , (OCH 2 CH 2 ) 2 , (OCH 2 CH 2 ) 3 , or (CH 2 ) m1 in which m1 is 2-5, Y 1 is a direct bond or O, w1 is 0 or 1, and D 1 is H.
  • Aryl acrylic monomers of formula (II) can be prepared from monofunctional polyphenyl ethers (i.e., ones with one functional group such as hydroxyl, amino, or carboxyl groups).
  • a monofunctional OH-terminated poly(phenyl ether) is reacted with a (meth)acrylic acid derivative (such as acryloyl chloride, methacryloyl chloride, methacrylic anhydride, or an isocyanatoalkyl acrylate or methacrylate) under coupling reaction conditions known to a person skilled in the art.
  • a (meth)acrylic acid derivative such as acryloyl chloride, methacryloyl chloride, methacrylic anhydride, or an isocyanatoalkyl acrylate or methacrylate
  • Mono-amine and mono-carboxylic acid terminated polyphenyl ethers are functionalized in a similar manner using suitable (meth)acrylic acid derivatives.
  • Monofunctional terminated polyphenyl ethers can be prepared according to procedures described in literature (J. Org. Chem., 1960, 25 (9), pp 1590–1595).
  • any hydrophobic vinylic monomer can be used as a substitute for a hydrophobic acrylic monomer, so long as it comprises at least one H-bond acceptor such as ester bond, amide bond, carbonate bond, carbamate bond, ether bond, or combinations thereof.
  • hydrophobic monomers include vinyl alkanoates (any one of those described above in this application), vinyloxyalkanes (any one of those described above in this application), and combinations thereof.
  • a hydrophobic crosslinked acrylic material comprises repeating units of at least one vinylic crosslinking agent. Any suitable vinyl crosslinking agents can be used in the invention.
  • vinylic cross-linking agents include without limitation: acrylic crosslinking agents (crosslinkers) (any one of those described later in this application), allyl methacrylate, allyl acrylate, an aryl crosslinking agent (e.g., divinylbenzene, 2-methyl-1,4-divinylbenzene, bis(4-vinylphenyl)methane, 1,2-bis(4- vinylphenyl)ethane, etc.), triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, 1,2,4- trivinylcyclohexane, or combinations thereof.
  • acrylic crosslinking agents crosslinkers
  • allyl methacrylate e.g., 2-methyl-1,4-divinylbenzene, bis(4-vinylphenyl)methane, 1,2-bis(4- vinylphenyl)ethane, etc.
  • aryl crosslinking agent e.g., divinylbenzene,
  • the hydrophobic crosslinked acrylic material comprises repeating units of at least one acrylic crosslinking agent (any one of those described later in this application).
  • the hydrophobic crosslinked acrylic material comprises repeating units of at least one aryl crosslinking agent (any one of those described later in this application).
  • the hydrophobic crosslinked acrylic material comprises repeating units of at least one vinyl-functional polysiloxane that comprises at least two vinyl groups each directly attached to one silicon atom and at least 15% by mole of siloxane units each having at least one phenyl substituent.
  • vinyl functional polysiloxanes examples include without limitation vinyl terminated polyphenylmethysiloxanes (e.g., PMV9925 from Gelest), vinylphenylmethyl terminated phenylmethyl-vinylphenylsiloxane copolymer (e.g., PVV-3522 from Gelest), vinyl terminated diphenylsiloxane-dimethylsiloxane copolymers (e.g., PDV-1625 from Gelest), or combinations thereof.
  • vinyl terminated polyphenylmethysiloxanes e.g., PMV9925 from Gelest
  • vinylphenylmethyl terminated phenylmethyl-vinylphenylsiloxane copolymer e.g., PVV-3522 from Gelest
  • vinyl terminated diphenylsiloxane-dimethylsiloxane copolymers e.g., PDV-1625 from Gelest
  • the vinyl-functional polysiloxane is vinyl terminated polyphenylmethysiloxanes (e.g., PMV9925 from Gelest), vinylphenylmethyl terminated phenylmethyl-vinylphenylsiloxane copolymer (e.g., PVV-3522 from Gelest), or combinations thereof.
  • An insert-forming composition can be prepared by mixing all polymerizable materials as described above in the desired proportions, together with one or more polymerization initiators (thermal polymerization initiators or photoinitiators) in the presence or preferably in the absence of a non-reactive organic solvent (i.e., a non-reactive diluent) as described later in this application.
  • thermal polymerization initiators can be used in the invention.
  • Suitable thermal polymerization initiators are known to the skilled artisan and comprise, for example peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.
  • thermal polymerization initiators include without limitation benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert- butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-Bis(tert-butylperoxy)-2,5- dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5- dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1- methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl- diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t- butylperoxy isopropyl carbonate, acet
  • the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).
  • Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, a benzoyl- phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, Germanium-based Norrish Type I photoinitiators (e.g., those described in US7605190).
  • benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylophosphine oxide; bis-(2,6-dichlorobenzoyl)- 4-N-propylphenyl-phosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide.
  • Reactive photoinitiators which can be incorporated, e.g., into a macromer or can be used as a special monomer are also suitable. Examples of reactive photoinitiators are those disclosed in EP632329.
  • the bulk hydrogel material (formed from a lens- forming composition) can be a non-silicone hydrogel material (any one of those described later in this application), or preferably a silicone hydrogel material (any one of those described later in this application).
  • a non-silicone hydrogel material can be formed from a polymerizable composition (such as one for forming a non-silicone hydrogel contact lens).
  • a polymerizable composition for forming a non-silicone hydrogel material is either (1) a monomer mixture comprising (a) at least one hydrophilic vinylic monomer (e.g., hydroxyl-containing vinylic monomer, N-vinylpyrrolidone, or combinations thereof) and (b) at least one component selected from the group consisting of a crosslinking agent, a hydrophobic vinylic monomer, a free-radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinylic monomer, a high-energy-violet-light (“HEVL”) absorbing vinylic monomer, a visibility tinting agent, and combinations thereof; or (2) an aqueous solution comprising one or more water-soluble prepolymers and at least one component selected from the group consisting of hydrophilic vinylic monomer, a crosslinking agent, a hydrophobic vinylic monomer, a lubricating agent (or so-called internal wetting agents incorporated in a lens formulation), a hydrophil
  • water-soluble prepolymers include without limitation: a water-soluble crosslinkable poly(vinyl alcohol) prepolymer described in U.S. Pat. Nos.5583163 and 6303687; a water-soluble vinyl group-terminated polyurethane prepolymer described in U.S. Pat. No.6995192; derivatives of a polyvinyl alcohol, polyethyleneimine or polyvinylamine, which are disclosed in U.S. Pat. No.5849841; a water-soluble crosslinkable polyurea prepolymer described in U.S. Pat.
  • Examples of commercial non-silicone hydrogel contact lenses include, without limitation, alfafilcon A, acofilcon A, deltafilcon A, etafilcon A, focofilcon A, helfilcon A, helfilcon B, hilafilcon B, hioxifilcon A, hioxifilcon B, hioxifilcon D, methafilcon A, methafilcon B, nelfilcon A, nesofilcon A, ocufilcon A, ocufilcon B, ocufilcon C, ocufilcon D, omafilcon A, phemfilcon A, polymacon, samfilcon A, telfilcon A, tetrafilcon A, and vifilcon A.
  • a non-silicone hydrogel material comprises at least 50% by mole of repeating units of at least one hydroxyl-containing vinylic monomer, preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N- 2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl
  • a silicone hydrogel material can be formed from a polymerizable composition (such as one for forming a silicone hydrogel contact lens).
  • a polymerizable composition such as one for forming a silicone hydrogel contact lens.
  • Numerous polymerizable compositions for forming silicone hydrogel materials have been described in numerous patents and patent applications published by the filing date of this application and have been used in producing commercial SiHy contact lenses.
  • Examples of commercial SiHy contact lenses include, without limitation, asmofilcon A, balafilcon A, comfilcon A, delefilcon A, efrofilcon A, enfilcon A, fanfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, smafilcon A, somofilcon A, and stenfilcon A. They can be used as a lens-forming composition of the invention.
  • a silicone hydrogel material comprises (a) repeating units of at least one first polysiloxane vinylic crosslinker comprising hydrophilized siloxane units each having one methyl substituent and one organic radical including at least one H-bond donor (preferably hydroxyl groups) and (b) repeating units of at least one hydrophilic vinylic monomer, wherein the content of said at least one H-bond donor is at least about 0.8 meq/g (preferably at least about 1.0 meq/g, more preferably at least about 1.2 meq/g, even more preferably at least about 1.4 meq/g) relative to the molecular weight of said at least one first polysiloxane vinylic crosslinker.
  • any polysiloxane vinylic crosslinkes can be used in the invention as the first polysiloxane vinylic crosslinkers, so long as they comprises hydrophilized siloxane units each having one methyl substituent and one organic radical having at least one H-bond donor (preferably hydoxyl group).
  • Examples of a class of preferred polysiloxane vinylic crosslinkers are di-(meth)acryloyloxy-terminated polysiloxane vinylic crosslinkers each having dimethylsiloxane units and hydrophilized siloxane units each having one methyl substituent and one monovalent C 4 –C 40 organic radical substituent having 2 to 6 hydroxyl groups, more preferably a polysiloxane vinylic crosslinker of formula (G), as described later in this application. They can be prepared according to the procedures disclosed in U.S. Pat. No.10081697. Any hydrophilic vinylic monomers can be used in the invention.
  • hydrophilic vinylic monomers examples include alkyl (meth)acrylamides (as described later in this application), hydroxyl-containing acrylic monomers (as described below), amino-containing acrylic monomers (as described later in this application), carboxyl-containing acrylic monomers (as described later in this application), N-vinyl amide monomers (as described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group connected to the pyrrolidone ring at 3- or 5- position) (as described later in this application), acrylic monomers having a C 1 -C 4 alkoxyethoxy group (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphorylcholine-containing vinylic monomers(as described later in this application) , N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyvin
  • the silicone hydrogel material can further comprise repeating units of a silicone-containing vinylic monomer and/or a second polysiloxane vinylic crosslinker (other than the first polysiloxane vinylic crosslinker).
  • a silicone-containing vinylic monomer can be any silicone-containing vinylic monomer known to a person skilled in the art.
  • silicone-containing vinylic monomers include without limitation vinylic monomers each having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, polysiloxane vinylic monomers, 3-methacryloxy propylpentamethyldisiloxane, t- butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.
  • Preferred polysiloxanes vinylic monomers including those of formula (M1) are described later in this application and can be obtained from commercial suppliers (e.g., Shin- Etsu, Gelest, etc.); prepared according to procedures described in patents, e.g., U.S. Pat.
  • Preferred silicone-containing vinylic monomers each having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, including those of formula (M2), are described later in this application and can be obtained from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.) or can be prepared according to procedures described in U.S. Pat. Nos.5070215, 6166236, 7214809, 8475529, 8658748, 9097840, 9103965, and 9475827. Any suitable polysiloxane vinylic crosslinkers can be used in the invention as the second polysiloxane vinylic crosslinkers.
  • polysiloxane vinylic crosslinkers as the second polysiloxane vinylic crosslinker are di-(meth)acryloyl-terminated polydimethyl-siloxanes; di-vinyl carbonate-terminated polydimethylsiloxanes; di-vinyl carbamate-terminated polydimethylsiloxane; N,N,N',N'-tetrakis(3-methacryloxy-2- hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane; polysiloxane- containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in US 5,760,100; polysiloxane-containing macromers disclosed in U.S.
  • One class of preferred polysiloxane vinylic crosslinkers as the second polysiloxane vinylic crosslinker are vinylic crosslinkers each of which comprises one sole polydiorganosiloxane segment and two terminal (meth)acryloyl groups, which can be obtained from commercial suppliers; prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with a di-amino-terminated polydimethylsiloxane or a di-hydroxyl- terminated polydimethylsiloxane; prepared by reacting isocyanatoethyl (meth)acrylate with di-hydroxyl-terminated polydimethylsiloxanes prepared by reacting an amino-containing acrylic monomer with di-carboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (a carbodiimide); prepared by reacting a carboxyl-containing acrylic monomer
  • polysiloxane vinylic crosslinkers as the second polysiloxane vinylic crosslinker are chain-extended polysiloxane vinylic crosslinkers each of which has at least two polydiorganosiloxane segments linked by a linker between each pair of polydiorganosiloxane segments and twe terminal ethylenically unsaturated groups, which can be prepared according to the procedures described in U.S. Pat. Nos.5034461, 5416132, 5449729, 5760100, 7423074, 8529057, 8835525, 8993651, 10301451, and 10465047.
  • the silicone hydrogel material can also comprise repeating units of one or more hydrophobic non-silicone vinylic monomers.
  • preferred hydrophobic non-silicone vinylic monomers can be non-silicone hydrophobic acrylic monomers (methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylonitrile, etc.), fluorine-containing acrylic monomers (e.g., perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, perfluoro-substituted-C 2 -C 12 alkyl (meth)acrylates described below, etc.), vinyl alkanoates (e.g., vinyl acetate, vinyl
  • perfluoro-substituted-C 2 -C 12 alkyl (meth)acrylates can be used in the invention.
  • perfluoro-substituted-C 2 -C 12 alkyl (meth)acrylates include without limitation 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoro-iso- propyl (meth)acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and combinations thereof.
  • the silicone hydrogel material can also comprise repeating units of one or more non-silicone vinylic crosslinkers. Examples of preferred non-silicone vinylic cross-linking agents are described later in this application.
  • the silicone hydrogel material can also comprises repeating units of other polymerizable materials, such as, a UV-absorbing vinylic monomer, a UV/high-energy-violet-light (“HEVL”) absorbing vinylic monomer, polymerizable photochromic compound, a polymerizable tinting agent (polymerizable dye), or combinations thereof, as known to a person skilled in the art.
  • UV-absorbing vinylic monomers and UV/HEVL-absorbing vinylic monomers can be used in a polymerizable composition for preparing a preformed SiHy contact lens of the invention.
  • preferred UV-absorbing and UV/HEVL-absorbing vinylic monomers include without limitation : 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamido methyl- 5-tert octylphenyl) benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5- chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'- hydroxy-5'-methacryloxypropyl-3'-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-
  • the polymerizable composition comprises about 0.1% to about 3.0%, preferably about 0.2% to about 2.5%, more preferably about 0.3% to about 2.0%, by weight of one or more UV-absorbing vinylic monomers, related to the amount of all polymerizable components in the polymerizable composition.
  • photochromic vinylic monomers examples include polymerizable naphthopyrans, polymerizable benzopyrans, polymerizable indenonaphthopyrans, polymerizable phenanthropyrans, polymerizable spiro(benzindoline)-naphthopyrans, polymerizable spiro(indoline)benzopyrans, polymerizable spiro(indoline)-naphthopyrans, polymerizable spiro(indoline)quinopyrans, polymerizable spiro(indoline)-pyrans, polymerizable naphthoxazines, polymerizable spirobenzopyrans; polymerizable spirobenzopyrans, polymerizable spirobenzothiopyrans, polymerizable naphthacenediones, polymerizable spirooxazines, polymerizable spiro(indoline)naph
  • the silicone hydrogel material comprises at least about 5% (preferably at least about 10%, more preferably at least about 15%, even more preferably at least about 20%, most preferably at least about 25%) by weight of repeating units of the first polysiloxane vinylic crosslinker.
  • the silicone hydrogel material has an equilibrium water content (i.e., in fully hydrated state or when being fully hydrated) of from about 20% to about 70% (preferably from about 20% to about 65%, more preferably from about 25% to about 65%, even more preferably from about 30% to about 60%) by weight, an oxygen permeability of at least about 40 barrers (preferably at least about 60 barrers, more preferably at least about 80 barrers, more preferably at least about 100 barrers), and a modulus (i.e., Young's modulus) of about 1.5 MPa or less (preferably from about 0.2 MPa to about 1.2 MPa, more preferably from about 0.3 MPa to about 1.1 MPa, even more preferably from about 0.4 MPa to about 1.0 MPa).
  • an equilibrium water content i.e., in fully hydrated state or when being fully hydrated
  • an oxygen permeability preferably at least about 40 barrers (preferably at least about 60 barrers, more preferably at least about 80 barrers, more preferably at least about 100
  • a lens-forming composition or an insert-forming composition can be a solventless clear liquid prepared by mixing all polymerizable components (or materials) and other necessary component(or materials) or a solution prepared by dissolving all of the desirable components (or materials) in any suitable solvent, such as, a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents, as known to a person skilled in the art.
  • suitable solvent such as, a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents, as known to a person skilled in the art.
  • solvent refers to a chemical that cannot participate in free-radical polymerization reaction (any of those solvents as described later in this application).
  • a solventless polymerizable composition typically comprises at least one blending vinylic monomer as a reactive solvent for dissolving all other polymerizable components. Examples of preferred blending vinylic monomers are described later in this application. Preferably, methyl methacrylate is used as a blending vinylic monomer in preparing a solventless polymerizable composition.
  • Suitable solvents include acetone, methanol, cyclohexane, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n- butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol
  • More preferred organic solvents include without limitation methanol, ethanol, 1-propanol, isopropanol, sec-butanol, tert-butyl alcohol, tert-amyl alcohol, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl propyl ketone, ethyl acetate, heptane, methylhexane (various isomers), methylcyclohexane, dimethylcyclopentane (various isomers), 2,2,4-trimethylpentane, and mixtures thereof.
  • the insert-forming composition and the lens-forming composition can be introduced into the insert-molding cavity and the lens-molding cavity respectively according any techniques known to a person skilled in the art.
  • the curing of a polymerizable composition within the insert-molding or lens-molding cavity of a mold can be carried out thermally (i.e., by heating) or actinically (i.e., by actinic radiation, e.g., UV radiation and/or visible radiation) to activate the polymerization initiators.
  • actinic polymerization of the polymerizable composition in a mold can be carried out by irradiating the closed mold with the polymerizable composition therein with an UV or visible light, according to any techniques known to a person skilled in the art.
  • the thermal polymerization of the polymerizable composition in a mold can be carried out conveniently in an oven at a temperature of from 25 to 120°C and preferably 40 to 100°C, as well known to a person skilled in the art.
  • the reaction time may vary within wide limits, but is conveniently, for example, from 1 to 24 hours or preferably from 2 to 12 hours. It is advantageous to previously degas the silicone-hydrogel-lens-forming composition and to carry out said copolymerization reaction under an inert atmosphere, e.g., under N 2 or Ar atmosphere.
  • the steps of opening a mold i.e., separating the male mold half from the female mold half with the unprocessed embedded silicone hydrogel contact lens attached onto one of the male and female mold halves
  • delensing i.e., removing the unprocessed embedded silicone hydrogel contact lens from the lens-adhered mold half
  • the unprocessed embedded hydrogel contact lens is delensed, it typically is extracted with an extraction medium as well known to a person skilled in the art.
  • the extraction liquid medium is any solvent capable of dissolving the diluent(s), unpolymerized polymerizable materials, and oligomers in the unprocessed embedded silicone hydrogel contact lens.
  • Water any organic solvents known to a person skilled in the art, or a mixture thereof can be used in the invention.
  • the organic solvents used extraction liquid medium are water, a buffered saline, a C 1 -C 3 alkyl alcohol, 1,2-propylene glycol, a polyethyleneglycol having a number average molecular weight of about 400 Daltons or less, a C 1 -C 6 alkylalcohol, or combinations thereof.
  • the extracted embedded hydrogel contact lens can then be hydrated according to any method known to a person skilled in the art.
  • the hydrated embedded hydrogel contact lens can further subject to further processes, such as, for example, surface treatment, packaging in lens packages with a packaging solution which is well known to a person skilled in the art; sterilization such as autoclave at from 118 to 124°C for at least about 30 minutes; and the like.
  • Lens packages (or containers) are well known to a person skilled in the art for autoclaving and storing a soft contact lens. Any lens packages can be used in the invention.
  • a lens package is a blister package which comprises a base and a cover, wherein the cover is detachably sealed to the base, wherein the base includes a cavity for receiving a sterile packaging solution and the contact lens.
  • Lenses are packaged in individual packages, sealed, and sterilized (e.g., by autoclave at about 120°C or higher for at least 30 minutes under pressure) prior to dispensing to users.
  • a person skilled in the art will understand well how to seal and sterilize lens packages.
  • a method for producing embedded hydrogel contact lenses comprising the steps of: (1) obtaining a magnetized insert which comprises a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the insert is made of a polymeric material and comprises magnetic particles; (2) obtaining a lens mold, wherein the lens mold comprises a female mold half having a first molding surface and a male mold half having a second molding surface, wherein the female and male mold halves are configured to receive each other such that a mold cavity is formed between the first and second molding surfaces when the mold is closed; (3) in no particular order, placing the magnetized insert in the lens mold and introducing a lens-forming composition in the lens mold, wherein the magnetized insert is immersed in the lens-forming composition in the lens mold and centered and held in position in the lens mold by using a magnet which is place below the lens mold; (4) curing the lens-forming composition in the lens mold while holding the magnetized insert centered in the lens mold by the magnet to form an unprocessed embedded hydrogel contact lens that comprise a bulk
  • An embedded hydrogel contact lens comprising: an anterior surface, an opposite posterior surface, a bulk hydrogel material, and a magnetized insert embedded in the bulk hydrogel material, wherein the magnetized insert is made of a polymeric material and comprises magnetic particles, wherein the magnetized insert has a front surface, an opposite back surface and a diameter up to about 13.0 mm, wherein the magnetized insert is located in a central portion of the embedded hydrogel contact lens, wherein the embedded hydrogel contact lens is not susceptible to delamination as demonstrated by being free of bubble that can be observed under microscopy at interfaces between the insert and the bulk material within the embedded silicone hydrogel contact lens after being autoclaved in a packaging solution in a sealed package, wherein the packaging solution is a buffered saline having a pH of 7.1 ⁇ 0.2.
  • the magnetized insert comprises the magnetic particles which are distributed in the polymeric material of the magnetized insert.
  • the magnetized insert comprises a magnetic coating on one of the front and back surfaces, wherein the magnetic coating comprises the magnetic particles.
  • the magnetized insert comprises a magnetic color image printed on one of the front and back surfaces with at least one ink comprising magnetic particles, wherein the magnetic color image is comprises the magnetic particles.
  • the magnetic color image comprises an annular ring.
  • the polymeric material of the magnetized insert comprises repeating units of at least one polymerizable photochromic compound (i.e., photochromic vinylic monomer), at least one UV-absorbing vinylic monomer, at least one UV/HEVL-absorbing vinylic monomer, at least one fluorescent vinylic monomer, or combinations thereof.
  • the magnetized insert comprises at least one color-filtering material for correcting color blindness, a diffractive material, a high refractive-index material, or combinations.
  • the polymeric material of the magnetized insert is a hard plastics.
  • any one of embodiments 1-3 and 5-10 or the embedded hydrogel contact lens of any one of embodiments 4-10 wherein the polymeric material of the magnetized insert is a crosslinked silicone polymer that has three-dimensional polymer networks, is insoluble in water, and has an equilibrium water content of about 5% or less (preferably about 3% or less, more preferably about 2% or less) by weight.
  • the polymeric material of the magnetized insert is a hydrophobic crosslinked acrylic material that has an equilibrium water content of less than 5% by weight and comprises at least 55% by mole of repeating units of one or more acrylic monomers and/or one or more acrylic crosslinker and at least about 6% by mole of repeating units of at least one vinylic crosslinking agent.
  • the hydrophobic crosslinked acrylic material has an equilibrium water content of about 4% or less by weight.
  • the hydrophobic crosslinked acrylic material has an equilibrium water content of about 3% or less by weight. 19.
  • the method or embedded hydrogel contact lens of any one of embodiments 16 to 19, wherein the hydrophobic crosslinked acrylic material comprises at least about 65% by mole of repeating units of said one or more acrylic monomers and/or said one or more acrylic crosslinker. 22.
  • the crosslinked polymeric material comprises at least about 8% by mole of repeating units of said at least one vinylic crosslinking agent.
  • the hydrophobic crosslinked acrylic material comprises at least about 10% by mole of repeating units of said at least one vinylic crosslinking agent. 25.
  • said at least one acrylic crosslinking agent is ethylene glycol dimethacrylate; ethylene glycol diacrylate; 1,3-propanediol diacrylate; 1,3-propanediol dimethacrylate; 2,3-propanediol diacrylate; 2,3-propanediol dimethacrylate; 1,4-butanediol dimethacrylate; 1,4- butanediol diacrylate; 1,5-pentanediol dimethacrylate; 1,5-pentanediol diacrylate; 1,6- hexanediol dimethacrylate; 1,6-hexanediol diacrylate; diethylene glycol dimethacrylate; diethylene glycol diacrylate; triethylene glycol dimethacrylate; triethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tetraethylene glycol diacrylate; N
  • the hydrophobic crosslinked acrylic material comprises repeating units of at least one non-silicone hydrophobic acrylic monomer.
  • 33. The method or embedded hydrogel contact lens of any one of embodiments 16 to 32, wherein the hydrophobic crosslinked acrylic material comprises repeating units of at least one fluorine-containing acrylic monomer. 34.
  • the method or embedded hydrogel contact lens of embodiment 36 wherein said at least polysiloxane vinylic crosslinker comprises at least 60% by mole of siloxane units each having at least one phenyl substituent.
  • said at least polysiloxane vinylic crosslinker comprises at least 90% by mole of siloxane units each having at least one phenyl substituent.
  • said at least polysiloxane vinylic crosslinker comprises three or more vinylphenylsiloxane units each having at least one phenyl substituent and one vinyl substituent. 41.
  • the method or embedded hydrogel contact lens of embodiment 36 wherein said at least polysiloxane vinylic crosslinker comprises one or more vinyl terminated polyphenylmethysiloxanes, one or more vinylphenylmethyl terminated phenylmethyl- vinylphenylsiloxane copolymers, one or more vinyl terminated diphenylsiloxane- dimethylsiloxane copolymers, or combinations thereof.
  • said at least polysiloxane vinylic crosslinker comprises one or more vinyl terminated polyphenylmethysiloxanes.
  • the method or embedded hydrogel contact lens of embodiment 36 wherein said at least polysiloxane vinylic crosslinker comprises one or more vinylphenylmethyl terminated phenylmethyl-vinylphenylsiloxane copolymers.
  • said at least one aryl acrylic monomer comprises at least one vinylic monomer selected from the group consisting of 2-ethylphenoxy acrylate; 2-ethylphenoxy methacrylate; phenyl acrylate; phenyl methacrylate; benzyl acrylate; benzyl methacrylate; 2-phenylethyl acrylate; 2-phenylethyl methacrylate; 3-phenylpropyl acrylate; 3-phenylpropyl methacrylate; 4-phenylbutyl acrylate; 4-phenylbutyl methacrylate; 4-methylphenyl acrylate; 4-methylphenyl methacrylate; 4-methylbenzyl acrylate; 4-methylbenzyl methacrylate; 2-(2-methylphenyl)ethyl acrylate; 2-(2-methylphenyl)ethyl methacrylate; 2-(3-methylphenyl)ethyl acrylate;
  • hydrophobic crosslinked acrylic material comprises repeating units of at least one hydrohobic vinylic monomer selected from the group consisting of a vinyl alkanoate, a vinyloxyalkane, styrene, vinyl toluene, vinyl chloride, vinylidene chloride, 1-butene, and combinations thereof.
  • hydrophobic insert is rigid.
  • said at least one hydroxyl-containing vinylic monomer is selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2- hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2- hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N- tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof.
  • the bulk hydrogel material is a silicone hydrogel material 54.
  • the method or embedded hydrogel contact lens of embodiment 53, wherein the bulk hydrogel material comprises (a) repeating units of at least one first polysiloxane vinylic crosslinker comprising hydrophilized siloxane units each having one methyl substituent and one organic radical including at least one H-bond donor and (b) repeating units of at least one hydrophilic vinylic monomer, wherein the content of said at least one H- bond donor is at least about 0.8 meq/g relative to the molecular weight of said at least one first polysiloxane vinylic crosslinker. 55.
  • the method or embedded hydrogel contact lens of embodiment 54 wherein said at least one first polysiloxane vinylic crosslinker comprises hydrophilized siloxane units each having one methyl substituent and one organic radical including at least one hydroxyl groups.
  • said at least one first polysiloxane vinylic crosslinker comprises hydrophilized siloxane units each having one methyl substituent and one organic radical including at least one hydroxyl groups.
  • the content of said at least one H-bond donor is at least about 1.0 meq/g relative to the molecular weight of said at least one first polysiloxane vinylic crosslinker.
  • 57. The method or embedded hydrogel contact lens of embodiment 54 or 55, wherein the content of said at least one H-bond donor is at least about 1.2 meq/g relative to the molecular weight of said at least one first polysiloxane vinylic crosslinker.
  • the method or embedded hydrogel contact lens of embodiment 54 or 55 wherein the content of said at least one H-bond donor is at least about 1.4 meq/g relative to the molecular weight of said at least one first polysiloxane vinylic crosslinker.
  • said at least one first polysiloxane vinylic crosslinker comprises a di- (meth)acryloyloxy-terminated polysiloxane vinylic crosslinker having dimethylsiloxane units and hydrophilized siloxane units each having one methyl substituent and one monovalent C 4 –C 40 organic radical substituent having 2 to 6 hydroxyl groups.
  • said at least one first polysiloxane vinylic crosslinker comprises comprises a vinylic crosslinker of formula (G) i n which: d1 is an integer of from 30 to 500 and d2 is an integer of from 1 to 75, provided that d2/d1 is from about 0.035 to about 0.15;
  • X 01 is O or NR IN in which R IN is hydrogen or C 1 -C 10 -alkyl; R I0 is hydrogen or methyl;
  • R I1 and R I2 independently of each other are a substituted or unsubstituted C 1 –C 10 alkylene divalent radical or a divalent radical of –R I4 –O–R I5 – in which R I4 and R I5 independently of each other are a substituted or unsubstituted C 1 –C 10 alkylene divalent radical;
  • RI3 is a monovalent radical of any one of formula (G-1) to (G-5) k
  • said at least one hydrophilic vinylic monomer comprises: (1) an alkyl (meth)acrylamide selected from the group consisting of (meth)acrylamide, N,N- dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N- propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, and combinations thereof; (2) a hydroxyl-containing acrylic monomer selected from the group consisting of N-2-hydroxylethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2- hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N- tris(hydroxymethyl)methyl (
  • said at least one hydrophilic vinylic monomer comprises N-2-hydroxylethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethy
  • the silicone hydrogel material comprises repeating units of at least one silicone-containing vinylic monomer selected from the group consisting of a vinylic monomer having a bis(trialkylsilyloxy)alkylsilyl group, a vinylic monomer having a tris(trialkylsilyloxy)silyl group, a polysiloxane vinylic monomer, 3-methacryloxy propylpentamethyldisiloxane, t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.
  • a silicone-containing vinylic monomer selected from the group consisting of a vinylic monomer having a bis(trialkylsilyloxy)alkylsilyl group, a vinylic monomer having a tris(trialkylsilyloxy)silyl group, a polysiloxane vinylic monomer, 3-methacryloxy propyl
  • the silicone hydrogel material comprises repeating units of at least one silicone-containing vinylic monomer of formula (M1) or (M2) in which: a M1 is zero or 1; R M0 is H or methyl; X M0 is O or NR M1 ; L M1 is a C 2 -C 8 alkylene a C 2 -C 8 alkylene divalent radical which has zero or one hydroxyl group; L M1 ” is C 3 -C 8 alkylene divalent radical which has zero or one hydroxyl group; X M1 is O, NR M1 , NHCOO, OCONH, CONR M1 , or NR M1 CO; R M1 is H or a C 1 -C 4 alkyl having 0 to 2 hydroxyl group; R t1 and R t2 independent of each other are a C 1 -C 6 alkyl; X M1 ' is O or NR 1 ; v1
  • silicone hydrogel material comprises tris(trimethylsilyloxy)silylpropyl (meth)acrylate, [3-(meth)acryloxy-2- hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2- hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2- hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2- hydroxypropyloxy)propyltris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)silylpropyl]- (meth)acrylamide, N-(2-hydroxy-3-(3- (bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)propyl)
  • the silicone hydrogel material comprises ⁇ -(meth)acryloxypropyl terminated ⁇ - C 1 -C 4 -alkyl terminated polydimethylsiloxane, ⁇ -(meth)acryloxy-2- hydroxypropyloxypropyl terminated ⁇ -C 1 -C 4 -alkyl terminated polydimethylsiloxane, ⁇ - (2-hydroxyl-methacryloxypropyloxypropyl)- ⁇ -C 1 -C 4 -alkyl-decamethylpentasiloxane, ⁇ - [3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ⁇ -C 1 -C 4 -alkyl terminated polydimethylsiloxane, ⁇ -[3-(meth)acryloxy-propyloxy-2- hydroxypropyloxypropyl]-terminated ⁇ -C 1 -C 4 -alkyl terminated polydimethylsiloxane,
  • the silicone hydrogel material comprises repeating units of at least one second polysiloxane vinylic crosslinker.
  • said at least one second polysiloxane vinylic crosslinker comprises a di-(meth)acryloyl- terminated polydimethylsiloxane, a di-vinyl carbonate-terminated polydimethylsiloxane; a di-vinyl carbamate-terminated polydimethylsiloxane; N,N,N',N'-tetrakis(3- methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane, or a combination thereof.
  • said at least one second polysiloxane vinylic crosslinker comprises: (1) a vinylic crosslinker which comprises one sole polydiorganosiloxane segment and two terminal ethylenically-unsaturated groups selected from the group consisting of (meth)acryloyloxy groups, (meth)acryloylamino groups, vinyl carbonate groups, vinylcarbamate groups; and/or (2) a chain-extended polysiloxane vinylic crosslinker which comprises at least two polydiorganosiloxane segment and a covalent linker between each pair of polydiorganosiloxane segments and two two terminal ethylenically-unsaturated groups selected from the group consisting of (meth)acryloyloxy groups, (meth)acryloylamino groups, vinyl carbonate groups, vinylcarbamate groups.
  • the silicone hydrogel material comprises repeating units of at least one non- silicone vinylic cross-linking agent.
  • said at least one non-silicone vinylic crossling agent comprises ethyleneglycol di- (meth)acrylate, diethyleneglycol di-(meth)acrylate, triethyleneglycol di-(meth)acrylate, tetraethyleneglycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di- (meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3- diyl)] di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3- diyl)] di-(meth)acrylate, ethylenebis[oxy
  • said at least one blending vinylic monomer comprises C 1 -C 10 alkyl (meth)acrylate, cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene (TMS), t-butyl styrene (TBS), trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, or combinations thereof.
  • the silicone hydrogel material comprises at least about 5% by weight of the first polysiloxane vinylic crosslinker.
  • the silicone hydrogel material comprises at least about 20% by weight of the first polysiloxane vinylic crosslinker.
  • 96 The method or embedded hydrogel contact lens of any one of embodiments 54 to 96, wherein the silicone hydrogel material has a modulus (i.e., Young's modulus) of from about 0.3 MPa to about 1.1 MPa.
  • Example 1 Oxygen Permeability Measurements Unless specified, the oxygen transmissibility (Dk /t), the intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) of an insert and an insert material are determined according to procedures described in ISO 18369-4. Equilibrium Water Content The equilibrium water content (EWC) of contact lenses is determined as follows.
  • Amount of water (expressed as percent by weight) present in a hydrated hydrogel contact lens, which is fully equilibrated in saline solution, is determined at room temperature. Quickly stack the lenses, and transfer the lens stack to the aluminum pan on the analytical balance after blotting lens in a cloth. The number of lenses for each sample pan is typically five (5). Record the pan plus hydrated weight of the lenses. Cover the pan with aluminum foil. Place pans in a laboratory oven at 100 ⁇ 2°C to dry for 16-18 hours. Remove pan plus lenses from the oven and cool in a desiccator for at least 30 minutes. Remove a single pan from the desiccator, and discard the aluminum foil. Weigh the pan plus dried lens sample on an analytical balance. Repeat for all pans.
  • the wet and dry weight of the lens samples can be calculated by subtracting the weight of the empty weigh pan.
  • Refractive Index The refractive index (RI) of inserts is determined by Abbe tranmission laboratory refractometer Reichert Abbe Mark III at 25°C. The inserts are fully equilibrated in PBS saline solution before measurement.
  • Elastic Modulus The storage modulus (Young's modulus) of inserts is determined using a TA RSA-G2 DMA (Dynamic Mechanical Analyzer). The insert is cut into a 3.08 mm wide strip using Precision Concept dry lens cutter. Five thickness values are measured within 6.5mm gauge length. The strip is mounted on the instrument with metal grips.
  • Oscillation temperature ramp test with a linear ramping rate at 2oC/minute from 10oC ⁇ 50oC is applied on the insert, the material response to increasing temperature is monitored at a constant frequency of 1 Hz, constant amplitude of 0.5% deformation and sampling rate of 10.0 pts/s.
  • Storage modulus (E'), loss modulus (E'') and tan ⁇ data are calculated by TRIOS software.
  • the elastic modulus of a silicone hydrogel material or contact lens is determined using a MTS insight instrument. The contact lens is first cut into a 3.12 mm wide strip using Precision Concept two stage cutter. Five thickness values are measured within 6.5mm gauge length.
  • the strip is mounted on the instrument grips and submerged in PBS (phosphate buffered saline) with the temperature controlled at 21 ⁇ 2 °C. Typically 5N Load cell is used for the test. Constant force and speed is applied to the sample until the sample breaks. Force and displacement data are collected by the TestWorks software. The elastic modulus value is calculated by the TestWorks software which is the slope or tangent of the stress vs. strain curve near zero elongation, in the elastic deformation region. Glass Transition Temperature Glass transition temperature (Tg) of the insert is defined as the peak of tan ⁇ from the dynamic temperature ramp test as described above.
  • PBS phosphate buffered saline
  • Delamination Embedded hydrogel contact lenses are examined for possible delamination either using Optimec instrument or Optical Coherence Tomography (OCT). Regardless of evaluation method, contact lenses are staged for a minimum of 12 hours at room temperature after autoclave run and prior to delamination study. After meeting required staging time, fully hydrated contact lens is placed in a “V” graticule assembly of Optimec instrument (Model JCF; OPTIMEC England). After the contact lens is settled under the influence of gravity, the front view of the contact lens is inspected carefully for any sign of circular pattern. Delamination displays as circular patterns in Optimec image. OCT (Spectral Domain Optical Coherence Tomography; Telesto-II; Thorlabs) could also be utilized to study delamination.
  • OCT Spectral Domain Optical Coherence Tomography; Telesto-II; Thorlabs
  • OCT allows non-invasive imaging of the contact lens to obtain high resolution cross-section image.
  • the contact lens is removed from its blister and is soaked into PBS solution for a minimum of 30 min to come to equilibrium. Then a cuvette with a “V” block feature will be filled approximately 3 ⁇ 4 with fresh PBS solution and the contact lens will be transferred to the cuvette using Q-tips. The lens will be allowed to freely float to the “V” shape at the bottom of the cuvette and the entire contact lens will be scanned in increment of 10 degree. Delamination appears as air pocket in interval surface of insert and carrier in OCT images.
  • PETA represents pentaerythritol tetraacrylate
  • TrisMA represents 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate
  • HFIPMA represents hexafluoroisopropyl methacrylate
  • NPGDMA represents neopentyl glycol dimethacrylate
  • DMA represents N,N-dimethyl acrylamide
  • HEMA represent 2-hydroxyethyl methacrylate
  • TEGDMA represent triethyleneglycol dimethacrylate
  • VAZO-52 represent 2-2'-Azobis(2,4-dimethylvaleronitrile)
  • VAZO 67 represents 2,2'-azobis(2- methylbutyronitrile)
  • RB247 is Reactive Blue 247
  • EGBE represents ethylene glycol butyl ether
  • PBS represents a phosphate-buffered saline which has a pH of 7.2 ⁇ 0.2 at 25°C and contains about 0.0
  • Example 2 Insert-Forming Compositions A base insert-forming compositions (i.e., Insert formulations) for making rigid hydrophobic inserts are prepared at room temperature in air by blending all the components (materials) as following: 45 weight part units of HFIPMA; 21 weight part units of NPGDMA; 45 weight part units of TrisMA; 0.5 weight part units of PETA; 3 weight part units of RB247; and 0.5 weight part units of Vazo-67. Three magnetized insert-forming compositions are then prepared by adding 1%, 0.1% and 0.02% by weight of magnetite (Sensient Cosmetics, black iron oxide, 2-5 ⁇ m).
  • Magnetite Sesient Cosmetics, black iron oxide, 2-5 ⁇ m
  • the black iron (II, III) oxide may also be incorporated by first forming a suspension in TRIS-MA or other monofunctional monomer that is part of the insert formulation.
  • the suspension is typically 5-50% black iron oxide (w/w) and is formed by ball milling methods.
  • Lens-Forming Compositions A lens-forming composition (i.e., SiHy lens formulation) is prepared at room temperature in air by blending all the components (materials) as following: 33 weight part units of H4; 17 weight part units of TrisMA; 24 weight part units of DMA; 1 weight part units of TEGDMA; 25.5 weight part units of EGBE; and 0.5 weight part units of Vazo-67.
  • the insert-forming compositions in the molds are thermally cured in the oven under the following conditions: ramp from room temperature to 55°C at a ramp rate of about 7°C/minute; holding at 55°C for about 30-40 minutes; ramp from 55°C to 80°C at a ramp rate of about 7°C/minute; holding at 55°C for about 30-40 minutes; ramp from 80°C to 100°C at a ramp rate of about 7°C/minute; and holding at 100°C for about 30-40 minutes.
  • the molds are opened and the molded inserts are removed from the insert-adhered mold halves. As control, non-magnetized inserts are obtained from the base insert-formulation (free of any magnetite).
  • a magnetized insert or a non-magnetized insert prepared above is placed in the central region of the molding surface of a female mold half (made of polypropylene), an amount of a SiHy lens formulation prepared above is dosed in the female mold half to immerse the magnetized insert, a polypropylene male mold half is then placed on top the female mold half, and the mold is closed securely.
  • a magnet (rare earth, SmCo, applied field 50-2000 Gauss) is placed below the female mold half to center the magnetized insert and hold it in position in the closed mold.
  • the closed mold with a magnetized insert immersed in a SiHy lens formulation therein are thermally cured in the oven under the following conditions: ramp from room temperature to 55°C at a ramp rate of about 7°C/minute; holding at 55°C for about 30-40 minutes; ramp from 55°C to 80°C at a ramp rate of about 7°C/minute; holding at 55°C for about 30-40 minutes; ramp from 80°C to 100°C at a ramp rate of about 7°C/minute; and holding at 100°C for about 30-40 minutes.
  • the molds are opened and the molded unprocessed embedded hydrogel contact lenses are removed from the molds. Lens molds each with a molded unprocessed silicone hydrogel contact lens therein are mechanically opened.
  • the molded unprocessed embedded silicone hydrogel contact lens adhere to the male mold halves or female mold halves. Molded unprocessed embedded silicone hydrogel contact lenses adhered to male mold halves are delensed using ultrasonic unit; molded unprocessed embedded silicone hydrogel contact lenses adhered to female mold halves are delensed are manually from lens-adhered female mold halves.
  • the delensed unprocessed embedded silicone hydrogel contact lenses can be extracted with a mixture of 50:50 of propylene glycol:water.
  • the delensed unprocessed embedded silicone hydrogel contact lenses are subjected to the following extraction/hyradtion, coating, autoclave processes as follows.
  • the unprocessed embedded silicone hydrogel contact lenses are soaked in a bath containing deionized water or an aqueous solution of Tween 80 (500 PPM), for about 60 minutes, then in a bath containing an aqueous solution of polyacrylic acid (PAA, Mw 450K) at a concentration of ca.0.1% by weight at 40°C for about 120 minutes; then in a bath containing a PBS solution at room temperature for about 60 minutes; packed/sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) with 0.65 mL of a in-package-coating packaging saline which is prepared according to the procedure described in Example 19 of US8480227; and finally autoclaved for about 45 minutes at 121°C.
  • PAA polyacrylic acid
  • the resultant embedded SiHy contact lenses each have a hydrogel coating thereon.
  • Figure 1 shows images of the unprocessed embedded SiHy contact lens obtained before opening the mold.
  • Figure 1A shows that the magnetized insert (from a magnetized insert-forming composition including 1% by weight of magnetites) is centered by the magnet in the unprocessed embedded silicone hydrogel contact lens.
  • Figure 1B shows that the non- magnetized insert cannot be centered by the magnet as shown by the decentered insert.
  • the obtained embedded SiHy contact lenses are examined for delamination according to the procedures described in Example 1. No bubble is observed under microscopy at interfaces between the magnetized insert and the SiHy bulk material within the embedded silicone hydrogel contact lens, i.e., no delamination.
  • Example 3 This example illustrates that a magnetized insert A can be formed by printing a magnetic colored image (e.g., an annular ring around the edge of the insert) onto at least one of the front and back surfaces of an annular ring of magnetite around the edge of the insert.
  • a magnetic colored image e.g., an annular ring around the edge of the insert
  • This provides enough magnetic material to allow an external magnet to control the position of the magnetized insert during casting-molding of embedded SiHy contact lenses.
  • Binder Polymer The binder polymer is a silicone hydrogel copolymer and prepared according to a 2- step process as described in Example 2 of U.S. Pat. Appl. Pub. No.2017-0183520A1.
  • a reactive mixture of DMA (38.53 weight unit parts), TRISMA (24.49 weight unit parts), HEMA (10.10 weight unit parts), Betacon (21.47 weight unit parts), VAZO-52 (weight unit parts), and 2-mercaptoethanol (1.38 weight unit parts) in ethyl acetate (158 weight unit parts) as solvent are copolymerized.
  • the copolymerization reaction is carried out under nitrogen in ethyl acetate at 50°C for about 24 hours.
  • VAZO-52 is used to initiate the polymerization while 2-mercaptoethanol is used as a chain transfer agent.
  • the 2- mercaptoethanol chain transfer agent regulates molecular weight and prevents gelation during the polymerization process.
  • IEM isocyanatoethyl methacrylate
  • DBTDL dibutyltin dilaurate
  • An ink containing magnetite (Fe 3 O 4, Sensient Cosmetics, as described above, 2-5 ⁇ m particle size) is prepared to have a composition: 10% by weight of Black iron oxide (50%, dispersed in 1-propanol); 38% by weight of the binder solution prepared above; 1% by weight of Omnirad 754 (formerly Irgacure 754, 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2- oxo-2-phenylacetate) and 51% by weight of PrOH. It is understood that any photoinitiator may be used, preferably Omnirad 1173, more preferably Omnirad 2959).
  • the formulation is loaded into an ink cup mated to a stainless steel cliché plate with a ring pattern with outer diameter of 12.96 mm and an inner diameter of 4.95 mm:
  • Preparation of Magnetized Inserts Inserts (having a diameter of about 6-7 mm) are cast-molded from the base insert- forming composition (prepared in Example 2) according to the procedure described in Example 2.
  • a magnetic annular ring is printed onto the front surface of an insert with the ink (prepared above and having magnetic particles therein) around the edge of the insert by using a pad printing system similar to that described in Figure 2 of U.S. Pat. Appl. Pub. No. 2020/0376787 A1.
  • the number of prints on the insert varied from 1-20 to increase the amount of magnetic particles.
  • the print(s) is (are) cured using the UV Fusion lamp system at a belt speed of 20 feet per minute using the H-bulb (Heraeus Noblelight) to obtain megnetized inserts each having a magnetic annular ring thereon.
  • H-bulb Heraeus Noblelight
  • megnetized inserts each having a magnetic annular ring thereon.
  • Embedded silicone hydrogel contact lenses are prepared from the magnetized inserts prepared above and the silicone hydrogel lens formulation prepared in Example 2 according to the procedure described in Example 2. It is observed that the magnetized insert (with a magnetic annular ring printed thereon) can be centered in the embedded silicone hydrogel contact lens.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Eyeglasses (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Prostheses (AREA)

Abstract

L'invention concerne un procédé de fabrication de lentilles de contact en hydrogel incorporées ayant chacune un insert magnétisé qui comprend des particules magnétiques et est incorporé au centre dans le matériau d'hydrogel en vrac de la lentille de contact en hydrogel incorporée. Pendant le moulage, un insert magnétisé peut être centré et maintenu en position dans un moule de lentille à l'aide d'un aimant placé sous le moule de lentille. L'invention concerne également une lentille de contact en hydrogel incorporée produite à partir d'un procédé de l'invention.
EP22713749.4A 2021-03-24 2022-03-23 Procédé de fabrication de lentilles de contact en hydrogel incorporées Pending EP4313566A1 (fr)

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US202163165292P 2021-03-24 2021-03-24
PCT/IB2022/052672 WO2022201072A1 (fr) 2021-03-24 2022-03-23 Procédé de fabrication de lentilles de contact en hydrogel incorporées

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CN115155331B (zh) * 2022-06-14 2023-05-26 南京工业大学 丙烯酰氧基封端的pdms制备薄膜复合膜、制备方法和用途
US20240316886A1 (en) * 2023-03-22 2024-09-26 Alcon Inc. Method for making embedded hydrogel contact lenses

Family Cites Families (150)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536386A (en) 1967-10-27 1970-10-27 Morris Spivack Contact lens with simulated iris
US3679504A (en) 1968-04-05 1972-07-25 Ceskoslovenska Akademie Ved Method of forming color effects in hydrogel contact lenses and ophthalmic prostheses
US3712718A (en) 1970-10-23 1973-01-23 J Legrand Corneal contact lens
DE2313331C2 (de) 1973-03-17 1986-11-13 Merck Patent Gmbh, 6100 Darmstadt Eisenoxidhaltige Glimmerschuppenpigmente
US4343927A (en) 1976-11-08 1982-08-10 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer compositions
US4182822A (en) 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4136250A (en) 1977-07-20 1979-01-23 Ciba-Geigy Corporation Polysiloxane hydrogels
US4153641A (en) 1977-07-25 1979-05-08 Bausch & Lomb Incorporated Polysiloxane composition and contact lens
US4189546A (en) 1977-07-25 1980-02-19 Bausch & Lomb Incorporated Polysiloxane shaped article for use in biomedical applications
US4261875A (en) 1979-01-31 1981-04-14 American Optical Corporation Contact lenses containing hydrophilic silicone polymers
US4254248A (en) 1979-09-13 1981-03-03 Bausch & Lomb Incorporated Contact lens made from polymers of polysiloxane and polycyclic esters of acrylic acid or methacrylic acid
US4276402A (en) 1979-09-13 1981-06-30 Bausch & Lomb Incorporated Polysiloxane/acrylic acid/polcyclic esters of methacrylic acid polymer contact lens
US4268132A (en) 1979-09-24 1981-05-19 Neefe Charles W Oxygen generating contact lens
US4401371A (en) 1979-09-24 1983-08-30 Neefe Charles W Hydrogel oxygen generator with improved fluid flow
US4260725A (en) 1979-12-10 1981-04-07 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains
US4259467A (en) 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4355147A (en) 1981-02-26 1982-10-19 Bausch & Lomb Incorporated Polysiloxane with polycyclic modifier composition and biomedical devices
US4341889A (en) 1981-02-26 1982-07-27 Bausch & Lomb Incorporated Polysiloxane composition and biomedical devices
US4327203A (en) 1981-02-26 1982-04-27 Bausch & Lomb Incorporated Polysiloxane with cycloalkyl modifier composition and biomedical devices
US4444711A (en) 1981-12-21 1984-04-24 Husky Injection Molding Systems Ltd. Method of operating a two-shot injection-molding machine
US4661575A (en) 1982-01-25 1987-04-28 Hercules Incorporated Dicyclopentadiene polymer product
US4460534A (en) 1982-09-07 1984-07-17 International Business Machines Corporation Two-shot injection molding
US4486577A (en) 1982-10-12 1984-12-04 Ciba-Geigy Corporation Strong, silicone containing polymers with high oxygen permeability
US4472327A (en) 1983-01-31 1984-09-18 Neefe Charles W Method of making hydrogel cosmetic contact lenses
US4543398A (en) 1983-04-28 1985-09-24 Minnesota Mining And Manufacturing Company Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols
US4704017A (en) 1984-04-16 1987-11-03 Schering Corporation Process for manufacturing colored contact lenses
US4582402A (en) 1984-04-16 1986-04-15 Schering Corporation Color-imparting contact lenses
US4605712A (en) 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
US4744647A (en) 1984-12-04 1988-05-17 Lens Plus Co. Semi-opaque corneal contact lens or intraoccular lens and method of formation
US4833218A (en) 1984-12-18 1989-05-23 Dow Corning Corporation Hydrophilic silicone-organic copolymer elastomers containing bioactine agent
US4634449A (en) 1986-10-03 1987-01-06 International Hydron Corporation Opaque tinting process for contact lens
US4684538A (en) 1986-02-21 1987-08-04 Loctite Corporation Polysiloxane urethane compounds and adhesive compositions, and method of making and using the same
US4719657A (en) 1986-03-27 1988-01-19 Bausch & Lomb Incorporated Method of forming iris variegation patterns on contact lenses
DE3708308A1 (de) 1986-04-10 1987-10-22 Bayer Ag Kontaktoptische gegenstaende
CA1340939C (fr) 1987-02-02 2000-03-28 Ryojiro Akashi Compose photochromique
US5156726A (en) 1987-03-24 1992-10-20 Tdk Corporation Oxygen-generating electrode and method for the preparation thereof
US4837289A (en) 1987-04-30 1989-06-06 Ciba-Geigy Corporation UV- and heat curable terminal polyvinyl functional macromers and polymers thereof
JPH0199822A (ja) * 1987-10-13 1989-04-18 Mitsubishi Gas Chem Co Inc 合成樹脂成形品の製造法
US5070170A (en) 1988-02-26 1991-12-03 Ciba-Geigy Corporation Wettable, rigid gas permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
US4954587A (en) 1988-07-05 1990-09-04 Ciba-Geigy Corporation Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
US5034166A (en) 1988-07-21 1991-07-23 Allergan, Inc. Method of molding a colored contact lens
US5120121A (en) 1988-07-21 1992-06-09 Allergan, Inc. Colored lens
JPH0651795B2 (ja) 1988-09-16 1994-07-06 信越化学工業株式会社 メタクリル官能性ジメチルポリシロキサン
US4954586A (en) 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5070215A (en) 1989-05-02 1991-12-03 Bausch & Lomb Incorporated Novel vinyl carbonate and vinyl carbamate contact lens material monomers
US5034461A (en) 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5079319A (en) 1989-10-25 1992-01-07 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5010141A (en) 1989-10-25 1991-04-23 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
CS532490A3 (en) 1989-11-01 1992-10-14 Schering Corp Colored contact lens having a very natural appearance
JP2713788B2 (ja) 1989-12-22 1998-02-16 ティーディーケイ株式会社 酸素発生用電極及びその製造方法
JP3327471B2 (ja) 1991-09-12 2002-09-24 ボシュ アンド ロム インコーポレイテッド ぬれ性のシリコーンヒドロゲル組成物および方法
DE69211152T2 (de) 1991-11-05 1997-01-02 Bausch & Lomb Zusammensetzungen von benetzbaren siliconhydrogels und verfahren zu deren herstellung
US5310779A (en) 1991-11-05 1994-05-10 Bausch & Lomb Incorporated UV curable crosslinking agents useful in copolymerization
US5358995A (en) 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
JP3195662B2 (ja) 1992-08-24 2001-08-06 株式会社メニコン 眼用レンズ材料
JP2774233B2 (ja) 1992-08-26 1998-07-09 株式会社メニコン 眼用レンズ材料
JPH071418U (ja) * 1993-06-07 1995-01-10 昌弘 石田 磁性材料を入れたコンタクトレンズ
TW328535B (en) 1993-07-02 1998-03-21 Novartis Ag Functional photoinitiators and their manufacture
TW272976B (fr) 1993-08-06 1996-03-21 Ciba Geigy Ag
US5712356A (en) 1993-11-26 1998-01-27 Ciba Vision Corporation Cross-linkable copolymers and hydrogels
US5894002A (en) 1993-12-13 1999-04-13 Ciba Vision Corporation Process and apparatus for the manufacture of a contact lens
US5843346A (en) 1994-06-30 1998-12-01 Polymer Technology Corporation Method of cast molding contact lenses
US5760100B1 (en) 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US5665840A (en) 1994-11-18 1997-09-09 Novartis Corporation Polymeric networks from water-soluble prepolymers
TW349967B (en) 1995-02-03 1999-01-11 Novartis Ag Process for producing contact lenses and a cross-linkable polyvinylalcohol used therefor
ATE178414T1 (de) 1995-02-03 1999-04-15 Novartis Ag Vernetzte polymere enthaltend ester- oder amidgruppen
FR2743154B1 (fr) 1995-12-29 1998-03-06 Essilor Int Lentille oculaire artificielle multifocale a transparence variable avec l'eclairement
US5793466A (en) 1996-08-27 1998-08-11 Moncada; Juliette R. Eye color highlighting contact lens
KR20000052663A (ko) 1996-10-21 2000-08-25 한스 루돌프 하우스, 헨리테 브룬너, 베아트리체 귄터 가교결합성 중합체
TW425403B (en) 1997-02-04 2001-03-11 Novartis Ag Branched polyurethane (meth)acrylate prepolymers, opthal-mic mouldings derived therefrom and processes for their manufacture
AU6821898A (en) 1997-02-21 1998-09-09 Novartis Ag Ophthalmic mouldings
FR2763070B1 (fr) 1997-05-06 1999-07-02 Essilor Int Nouveaux composes photochromiques spirooxazines, leur utilisation dans le domaine de l'optique ophtalmique
JP4616473B2 (ja) 1997-09-16 2011-01-19 ノバルティス アーゲー 架橋結合可能なポリ尿素ポリマー類
GB2333518A (en) 1998-01-26 1999-07-28 Laporte Industries Ltd Process for making black iron oxide pigment
US5962548A (en) 1998-03-02 1999-10-05 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US6022495A (en) 1998-07-10 2000-02-08 Transitions Optical, Inc. Photochromic benzopyrano-fused naphthopyrans
US6039913A (en) 1998-08-27 2000-03-21 Novartis Ag Process for the manufacture of an ophthalmic molding
ES2244213T3 (es) 1998-09-11 2005-12-01 Transitions Optical, Inc. Naftopiranos polialcoxilados polimerizables.
EP1002807A1 (fr) 1998-11-20 2000-05-24 Novartis AG Résine fonctionnalisée, dérivée de polyallylamine
US5981675A (en) 1998-12-07 1999-11-09 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
US6851805B2 (en) 1999-07-02 2005-02-08 E-Vision, Llc Stabilized electro-active contact lens
BR0013052A (pt) 1999-07-27 2002-04-09 Bausch & Lomb Metodo para preparar um hidrogel de pré-polimero de silicone; hidrogel contendo silicone; lente de contato e lente intraocular
US6348604B1 (en) 1999-09-17 2002-02-19 Ppg Industries Ohio, Inc. Photochromic naphthopyrans
US6296785B1 (en) 1999-09-17 2001-10-02 Ppg Industries Ohio, Inc. Indeno-fused photochromic naphthopyrans
ATE441132T1 (de) 1999-12-16 2009-09-15 Asahikasei Aime Co Ltd Zum tragen über lange zeiträume geeignete weiche kontaktlinsen
US6811259B2 (en) 2000-06-12 2004-11-02 Novartis Ag Printing colored contact lenses
DE10065761B4 (de) 2000-12-30 2005-01-20 Merck Patent Gmbh Plättchenförmige magnetische Partikel, ihre Herstellung und Verwendung
US7411008B2 (en) 2001-11-07 2008-08-12 Novartis Ag Ink formulations and uses thereof
US6995192B2 (en) 2002-08-14 2006-02-07 Novartis Ag Radiation-curable prepolymers
US7104648B2 (en) 2002-09-06 2006-09-12 Synergeyes, Inc. Hybrid contact lens system and method
US20040141150A1 (en) 2003-01-21 2004-07-22 Roffman Jeffrey H. Hybrid multifocal contact lenses
US20040186241A1 (en) 2003-03-20 2004-09-23 Gemert Barry Van Photochromic ocular devices
CA2535905A1 (fr) 2003-08-15 2005-02-24 E-Vision, Llc Systeme de lentille electro-active ameliore
WO2005028566A1 (fr) 2003-09-22 2005-03-31 Nippon Sheet Glass Company, Limited Pigment noir brillant, produit cosmetique, composition de revetement, composition de resine et composition d'encre contenant ledit pigment
US7977430B2 (en) 2003-11-25 2011-07-12 Novartis Ag Crosslinkable polyurea prepolymers
US7214809B2 (en) 2004-02-11 2007-05-08 Johnson & Johnson Vision Care, Inc. (Meth)acrylamide monomers containing hydroxy and silicone functionalities
US7278736B2 (en) 2004-02-25 2007-10-09 Novartis Ag Contact lenses imparting a vivacious appearance to the eye
KR101367538B1 (ko) 2004-08-27 2014-02-26 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 실리콘 히드로겔 콘택트 렌즈
JP4933448B2 (ja) 2004-12-29 2012-05-16 ボーシュ アンド ローム インコーポレイティド 生物医学装置用ポリシロキサンプレポリマー
US9052438B2 (en) 2005-04-08 2015-06-09 Johnson & Johnson Vision Care, Inc. Ophthalmic devices comprising photochromic materials with reactive substituents
US7556750B2 (en) 2005-04-08 2009-07-07 Transitions Optical, Inc. Photochromic materials with reactive substituents
US8158037B2 (en) 2005-04-08 2012-04-17 Johnson & Johnson Vision Care, Inc. Photochromic materials having extended pi-conjugated systems and compositions and articles including the same
US8038711B2 (en) 2005-07-19 2011-10-18 Clarke Gerald P Accommodating intraocular lens and methods of use
USRE46357E1 (en) 2006-06-30 2017-04-04 Hoya Corporation Photochromic film, photochromic lens comprising the same, and method of manufacturing photochromic lens
EP1905415B1 (fr) 2006-09-27 2009-07-01 Ivoclar Vivadent AG Compositions polymérisable avec acyl-germanium comme amorceurs
AR064985A1 (es) 2007-01-22 2009-05-06 E Vision Llc Lente electroactivo flexible
BRPI0807560A2 (pt) 2007-02-23 2014-07-01 Pixeloptics Inc Abertura oftálmica dinâmica
US7883207B2 (en) 2007-12-14 2011-02-08 Pixeloptics, Inc. Refractive-diffractive multifocal lens
US20090091818A1 (en) 2007-10-05 2009-04-09 Haddock Joshua N Electro-active insert
JP4976254B2 (ja) * 2007-10-17 2012-07-18 株式会社メニコン コンタクトレンズの製造方法
US8154804B2 (en) 2008-03-25 2012-04-10 E-Vision Smart Optics, Inc. Electro-optic lenses for correction of higher order aberrations
US7931832B2 (en) 2008-03-31 2011-04-26 Johnson & Johnson Vision Care, Inc. Ophthalmic lens media insert
US8211225B2 (en) 2008-04-09 2012-07-03 Sun Chemical Corp. Magnetic pigments and process of enhancing magnetic properties
US8922898B2 (en) 2008-09-04 2014-12-30 Innovega Inc. Molded lens with nanofilaments and related methods
US20100076553A1 (en) 2008-09-22 2010-03-25 Pugh Randall B Energized ophthalmic lens
US9296158B2 (en) 2008-09-22 2016-03-29 Johnson & Johnson Vision Care, Inc. Binder of energized components in an ophthalmic lens
US8348424B2 (en) 2008-09-30 2013-01-08 Johnson & Johnson Vision Care, Inc. Variable focus ophthalmic device
JP5720103B2 (ja) 2010-03-18 2015-05-20 東レ株式会社 シリコーンハイドロゲル、眼用レンズおよびコンタクトレンズ
US8697770B2 (en) 2010-04-13 2014-04-15 Johnson & Johnson Vision Care, Inc. Pupil-only photochromic contact lenses displaying desirable optics and comfort
WO2012013549A1 (fr) 2010-07-29 2012-02-02 Novartis Ag Lentilles de contact colorées et leur procédé de fabrication
KR101819873B1 (ko) 2010-07-30 2018-01-17 노파르티스 아게 가교된 친수성 코팅을 갖는 실리콘 히드로겔 렌즈
BR112013008221B1 (pt) 2010-10-06 2020-02-11 Alcon Inc. Pré-polímero processável em água, lente de contato de hidrogel de silicone e seu método de fabricação
JP5784131B2 (ja) 2010-10-06 2015-09-24 ノバルティス アーゲー ペンダント親水性基を持つ重合しうる鎖延長ポリシロキサン
US20120140167A1 (en) 2010-11-01 2012-06-07 Pixeloptics, Inc. Dynamic Changeable Focus Contact And Intraocular Lens
KR101906619B1 (ko) 2010-12-09 2018-10-10 메르크 파텐트 게엠베하 자성 안료
EP2652544B1 (fr) 2010-12-14 2020-08-19 Alcon Inc. Lentille de contact colorée
KR101743801B1 (ko) 2011-02-28 2017-06-05 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 허용가능한 수준의 에너지 손실을 갖는 실리콘 히드로겔 콘택트 렌즈
US9217813B2 (en) 2011-02-28 2015-12-22 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
US9889615B2 (en) 2011-03-18 2018-02-13 Johnson & Johnson Vision Care, Inc. Stacked integrated component media insert for an ophthalmic device
US10209534B2 (en) 2012-03-27 2019-02-19 Johnson & Johnson Vision Care, Inc. Increased stiffness center optic in soft contact lenses for astigmatism correction
US9176332B1 (en) 2012-10-24 2015-11-03 Google Inc. Contact lens and method of manufacture to improve sensor sensitivity
US20150305929A1 (en) * 2012-11-07 2015-10-29 Emmetrope Ophthalmics Llc Magnetic contact lenses and methods of treatment and diagnosis using the same
CA3030638C (fr) 2012-12-14 2020-09-15 Novartis Ag Monomeres vinyliques contenant un siloxane amphiphile et leurs utilisations
US9475827B2 (en) 2012-12-14 2016-10-25 Shin-Etsu Chemical Company, Ltd. Tris(trimethyl siloxyl)silane vinylic monomers and uses thereof
US9097840B2 (en) 2012-12-14 2015-08-04 Novartis Ag Amphiphilic siloxane-containing (meth)acrylamides and uses thereof
US8874182B2 (en) 2013-01-15 2014-10-28 Google Inc. Encapsulated electronics
US9977260B2 (en) 2013-03-15 2018-05-22 Johnson & Johnson Vision Care, Inc. Sealing and encapsulation in energized ophthalmic devices with annular inserts
US8974055B2 (en) 2013-03-15 2015-03-10 Johnson & Johnson Vision Care, Inc. Method and apparatus for encapsulating a rigid insert in a contact lens for correcting vision in astigmatic patients
US10025118B1 (en) * 2013-07-20 2018-07-17 David T. Markus Piezoelectric energy harvesting contact lens
US9731437B2 (en) 2013-11-22 2017-08-15 Johnson & Johnson Vision Care, Inc. Method of manufacturing hydrogel ophthalmic devices with electronic elements
US9846263B2 (en) 2013-11-26 2017-12-19 Novartis Ag Metal oxide dispersion and uses thereof
JP6470304B2 (ja) 2014-04-08 2019-02-13 ノバルティス アーゲー 酸素発生素子を内蔵する眼用レンズ
US10064977B2 (en) 2015-02-16 2018-09-04 Novartis Ag Wet-pack intraocular lens materials with high refractive index
MY197430A (en) 2015-12-15 2023-06-17 Alcon Inc Hydrophilized polydiorganosiloxane vinylic crosslinkers and uses thereof
JP6839295B2 (ja) 2016-10-11 2021-03-03 アルコン インク． 重合性ポリジメチルシロキサン−ポリオキシアルキレンブロックコポリマー
JP6859432B2 (ja) 2016-10-11 2021-04-14 アルコン インク． 鎖延長ポリジメチルシロキサンビニル架橋剤およびその使用
US10156736B2 (en) 2017-04-13 2018-12-18 Novartis Ag Colored contact lenses and method of making the same
CN107669400A (zh) * 2017-09-22 2018-02-09 苏州四海通仪器有限公司 用于按摩睑板腺的隐形眼镜及睑板腺按摩仪
US12064237B2 (en) * 2018-03-13 2024-08-20 Menicon Co., Ltd. Determination system, computing device, determination method, and program
EP3976362B1 (fr) 2019-05-28 2023-06-07 Alcon Inc. Procédé de fabrication de lentilles de contact en hydrogel de silicone colorées opaques

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TW202239578A (zh) 2022-10-16
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WO2022201072A1 (fr) 2022-09-29

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